JPH111064A - Sublimation type thermal transfer recording method and image receiving sheet for sublimation transfer - Google Patents

Abstract

(57) Abstract: Provided is a sublimation-type thermal transfer recording method in which a good printed image is obtained even when an image is formed using an n-times mode method, and the quality of the printed image is maintained for a long period of time. After forming an image on an image receiving sheet, the image is subjected to heat treatment by a thermal head via a thermal transfer sheet having a dye-free region or another heat treatment sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sublimation type thermal transfer recording method and an image receiving sheet for sublimation transfer.

[0002]

2. Description of the Related Art In recent years, the demand for full-color printers has been increasing year by year, and the recording methods of the full-color printer include an electrophotographic system, an ink-jet system, and a thermal transfer system. For this reason, the thermal transfer method has been attracting attention. In this thermal transfer method, (i) a recording medium having a transfer layer in which a coloring agent is dispersed in a heat-fusible substance and an image receiving sheet are superimposed, and an image is formed on the recording medium with a thermal head or a laser beam. (Ii) a heat-sensitive sublimable dye or a heat-migrating dye (hereinafter simply referred to as “sublimable dye”); ). A recording medium having a transfer layer containing) is superimposed on an image receiving sheet, and heat is applied imagewise to the recording medium, so that the sublimable dye of the transfer layer is sublimated or transferred onto the image receiving sheet. There is a sublimation type thermal transfer recording method of recording at least.

For recording a full-color image, the sublimation-type thermal transfer recording method (ii) is generally superior in terms of color tone fidelity. In this sublimation type thermal transfer recording method, in order to save the running cost of a thermal transfer body and a thermal transfer sheet as a recording medium, one thermal transfer body can be used for plural times of recording, or the traveling speed of the thermal transfer sheet is overlapped with this. Recording at a speed lower than the running speed of the dye receiving sheet (relative speed 1 / n, n> 1), so-called n
A double mode method has been proposed.

[0004] The conventional image-receiving sheet for sublimation transfer has insufficient durability such as storage stability over time, light resistance, plasticizer resistance, fingerprint resistance and friction resistance of the formed image. When stored in an environment or exposed to light such as sunlight, image quality and image density may be reduced. Recently,
It is considered that the sublimation type thermal transfer recording method is applied to various ID cards such as a driver's license and an identification card. In such a case, it is necessary to maintain clear recorded information for a long time. Therefore, extremely high durability is required.

As a means for solving such various problems, for example, an image receiving sheet for sublimation transfer on which an image is formed is prepared by bonding a transparent resin film containing a light deterioration inhibitor such as an ultraviolet absorber or an antioxidant to an adhesive. It has been proposed that the action of light or oxygen is suppressed or shielded by laminating through a layer. However, in this method, durability such as light resistance is improved to some extent, but the operation is complicated, and an apparatus such as a laminator is further required. This increases the cost and causes the dye to migrate to the adhesive layer and blur the image. And the like.

Further, after an image of a sublimable dye is formed on a single-layer or laminated image receiving layer of a sublimation transfer image receiving sheet, reheating is performed by a thermal head or the like to remove the sublimation dye existing on the surface of the image receiving layer. It diffuses and moves inside the image receiving layer,
Proposals aimed at improving plasticizer resistance and image stability have been proposed, for example, in JP-B-4-55870, JP-A-4-28.
No. 4291 and JP-A-9-66678, and a tentative effect is obtained on light resistance, plasticizer resistance and image stability. However, since the thermal head applies heat while scanning at a high temperature, even if the thermal sublimation transfer sheet is heated via the reheating area where the sublimable dye is not applied, the reheating area of the thermal sublimation transfer sheet is not heated. Unevenness due to heat is formed. Further, there is a problem that a portion to be scanned by heating of the thermal head is burned, the glossiness of the image on the image receiving sheet is reduced, and the image receiving sheet is curled.

Conventionally, as an image receiving sheet for sublimation type thermal transfer recording, a sheet having a dye receiving layer formed of a thermoplastic polyester resin or the like having a strong dyeing property on a sublimable dye is formed on a substrate. Have been. However, in the conventional image receiving sheet, fusing and sticking generated at the time of recording are not yet sufficient, and particularly when applied to the n-fold mode method, a strong frictional force is generated between the image receiving sheet and the heat-sensitive sublimation transfer sheet (recording medium). In addition, the recording sheet and the heat-sensitive sublimation transfer sheet are superimposed on each other, and the two are run at a constant speed. Higher heat resistance and lubricity are required.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to sublimate or transfer an image-wise sublimable dye onto a sublimation transfer image-receiving sheet, and then reheat it with a thermal head to obtain light resistance, While maintaining good plasticizer resistance and image stability, the image on the image receiving sheet has good gloss without burning the image receiving sheet, and it is suitable for reheating areas of heat treatment sheets and heat-sensitive sublimation transfer sheets. An object of the present invention is to provide a sublimation-type thermal transfer recording method that does not cause an abnormality. Another object of the present invention is to obtain a normal printed image without problems such as fusing, sticking, and sheet breakage during recording even in image formation. In particular, sublimation transfer that is effective when the n-times mode method is used. An object of the present invention is to provide an image receiving sheet.

[0009]

According to the present invention, first, a dye-receiving layer surface of a sublimation transfer image-receiving sheet having at least a dye-receiving layer on a substrate, and at least one or more ink layers on the substrate. After the image is formed on the image receiving sheet for sublimation transfer by superimposing the ink layer surface of the heat-sensitive sublimation transfer sheet having In the sublimation type thermal transfer recording method in which heat treatment is performed via a heat-sensitive sublimation transfer sheet having a region containing no dye or another heat treatment sheet, the applied energy Eb of the heat treatment is changed to the applied energy Ei during image formation.
A sublimation type thermal transfer recording method, wherein a heat treatment is performed to satisfy Ei> Eb.

Second, the applied energy Eb of the applied energy of the heat treatment is equal to the applied energy Ei during image formation.
The sublimation type thermal transfer recording method, wherein Ei> Eb ≧ 0.8Ei.

Third, the dye-receiving layer surface of a sublimation transfer image receiving sheet having at least a dye-receiving layer on a substrate and the ink layer surface of a heat-sensitive sublimation transfer sheet having at least one or more ink layers on a substrate. An image is formed on the image-receiving sheet for sublimation transfer by superposing and heating from the substrate side of the heat-sensitive sublimation transfer sheet, and then the image-receiving sheet for sublimation transfer is subjected to thermal sublimation transfer having an area containing no dye by a thermal head. In a sublimation transfer recording method in which a heat treatment is performed through a sheet or another heat treatment sheet, the length of a heat-sensitive sublimation transfer sheet having a region not containing the dye or another heat treatment sheet has an image area. And a sublimation type thermal transfer recording method characterized by being shorter than the length.

Fourth, the dye receiving layer surface of a sublimation transfer image receiving sheet having at least a dye receiving layer on a substrate, and the ink layer surface of a heat-sensitive sublimation transfer sheet having at least one or more ink layers on a substrate. An image is formed on the image-receiving sheet for sublimation transfer by superposing and heating from the substrate side of the heat-sensitive sublimation transfer sheet, and then the image-receiving sheet for sublimation transfer is subjected to thermal sublimation transfer having an area containing no dye by a thermal head. In a sublimation-type thermal transfer recording method in which a heat treatment is performed by an n-fold mode method via a sheet or another heat treatment sheet, a heat-sensitive sublimation transfer sheet having a region not containing the dye or another heat treatment sheet A sublimation type thermal transfer recording method, wherein the length b is b ≦ i with respect to the length i of the dye layer region of the thermosensitive sublimation transfer sheet. It is provided.

Fifth, in a sublimation transfer image receiving sheet having a dye receiving layer provided on a substrate and an over layer further provided on the dye receiving layer, the ASTM D
The coefficient of dynamic friction μ at 100 ° C. according to 1894 is 0.4
The sublimation transfer image-receiving sheet, wherein the number is less than 5, and the overlayer comprises a silicone resin and a lubricating substance.

Sixth, there is provided the fifth sublimation transfer image-receiving sheet, wherein the lubricating substance is a silicone graft copolymer.

Seventh, the fifth and sixth sublimation transfer image-receiving sheets are provided, wherein the content of the silicone resin in the overlayer is less than 85% by weight.

Eighth, there is provided the fifth, sixth, and seventh image receiving sheets for sublimation transfer, wherein the thickness of the over layer is 2 μm or less.

Ninth, there is provided the sixth image receiving sheet for sublimation transfer, wherein the binder resin of the silicone graft copolymer is a dyeable resin.

Tenthly, there is provided the fifth sublimation transfer image receiving sheet, wherein the over layer contains silicone oil.

Eleventh, the tenth sublimation transfer image-receiving sheet is provided, wherein the silicone oil is at least an epoxy-modified or unmodified silicone oil.

Twelfth, there is provided the tenth sublimation transfer image receiving sheet, wherein the amount of the silicone oil added is 3 to 50% by weight based on the resin of the over layer.

Thirteenth, the tenth sublimation transfer image-receiving sheet is provided, wherein the amount of the silicone oil added is 5 to 15% by weight based on the resin of the overlayer.

Fourteenth, the above tenth sublimation transfer image receiving method is characterized in that the overlayer forming solution contains a solvent compatible with silicone oil in an amount of 25% by weight or more of the total solvent of the overlayer forming solution. A sheet is provided.

Fifteenth, in the image receiving sheet for sublimation transfer which is provided with a dye receiving layer on a substrate and further provided with an over layer on the dye receiving layer, which is applied to the n-times mode method, There is provided an image receiving sheet for sublimation transfer, wherein the layer comprises a silicone resin, a lubricating substance and an ultraviolet absorber as main components.

Sixteenthly, the fifteenth sublimation transfer image-receiving sheet is provided, wherein the content of the ultraviolet absorber is 1 to 50% by weight based on the resin of the overlayer.

Seventeenthly, there is provided the first to sixth sublimation transfer image receiving sheets, wherein the substrate is a laminate in which a cushion layer is provided on paper.

Eighteenthly, the cushion layer is a bubble-containing plastic film, and the density D of the bubble-containing plastic film is D / Do ≦ 0.7 (Do is the density of a plastic film of the same material containing no bubbles). The seventeenth sublimation transfer image-receiving sheet is provided.

Nineteenthly, the fifteenth to eighteenth sublimation transfer image receiving sheets are provided, wherein a polyethylene layer is provided on the back side of the base.

Twentieth, the fifth to nineteenth sublimation transfer image receiving sheets are provided, wherein the substrate is a card substrate.

Twenty-first, the uppermost layer of the thermal transfer sheet or another heat-treating sheet having the dye-free region described in the above-mentioned first to fourth is a low-dyeing resin layer. Thermal sublimation transfer sheet or heat treatment sheet.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the sublimation type thermal transfer recording method, a sublimable dye in an ink layer of a thermal sublimation transfer sheet is transferred onto an image receiving layer of an image receiving sheet for sublimation transfer by heating to form an image. But,
Since the sublimable dye of this image is mostly present near the outer surface of the image receiving layer, the image quality during long-term storage deteriorates. In the present invention, the dye transferred to the image receiving sheet is pushed into the inside of the image receiving layer by subjecting the sublimable dye present on the image receiving layer surface to a heat treatment by a thermal head, and has a durability such as storage stability or plastic resistance. Improvement and further improvement in light resistance can be achieved.

The object of the present invention is achieved by performing the heat treatment of the present invention using a thermal head with the following applied energy. Ei> Eb More preferably, Ei> Eb ≧ 0.8Ei (Eb: applied energy for heat treatment, Ei: applied energy for image formation) When the applied energy for heat treatment is equal to or more than the applied energy for image formation, sublimation occurs. Heating the entire image area of the transfer image receiving sheet with equal energy places a considerable burden on the thermal head, which tends to shorten the life of the thermal head, and at the same time, the surface of the image receiving layer has a surface at the maximum energy of image formation. The image receiving layer resin is burned, causing various problems such as a reduction in image quality due to abnormal gloss reduction, a reheating sheet or the like having irregularities due to heat, and curling of the image receiving sheet. 8 of applied energy during image formation
If it is less than 0%, the sublimable dye existing near the outer surface of the image receiving layer will not be sufficiently pushed into the image receiving layer, and the effect of improving the durability such as storage stability over time and the light resistance tends to be lost. is there.

When the image formation using the thermal transfer sheet is performed by the n-fold mode method, it is preferable to perform the heat treatment by the n-fold mode method because it is advantageous in terms of cost. At this time, it is desirable that the length b of the heated area of the thermal transfer sheet having the area containing no dye is b ≦ i with respect to the length i of the dye layer area of the thermal transfer sheet. Where b =
When i (the length of the heated area of the thermal transfer sheet having the area containing no dye and the length of the dye layer area of the thermal transfer sheet are substantially equal), it means that the n value of the n-times mode method is equal. The glossiness of the image receiving sheet surface is better than when the processing is performed by the constant velocity mode method. This is because in the n-fold mode method, the relative speeds of the image receiving sheet and the thermal transfer sheet are different, and the surface of the image receiving sheet is rubbed. Also, b <i
Means that the n value at the time of the heat treatment is smaller than the n value at the time of image formation, and the glossiness is further improved;
It is also advantageous in terms of cost.

As the image-receiving sheet for sublimation transfer used in the sublimation-type thermal transfer recording method of the present invention, conventionally known ones can be used as long as they have at least a dye-receiving layer on a substrate.

In the sublimation transfer image-receiving sheet, a resin having high dyeing properties may be used to increase the image density, and a resin constituting the receiving layer may be a conventionally known material. For example, a polyester resin, a vinyl chloride resin, an acrylic resin, a polyurethane resin, a vinyl acetate resin, a polyamide resin and the like can be mentioned. At this time, the thickness of the receiving layer is preferably about 1 to 20 μm, particularly preferably 1 to 10 μm.

In the receiving layer, a filler, if necessary,
Known additives such as a surfactant, an ultraviolet absorber, an antioxidant, and a fluorescent brightener can be added in an amount of 5 to 60% by weight. Examples of the filler include white inorganic pigments such as silica, titanium oxide, and calcium carbonate, and organic pigments such as a fluororesin.

Examples of the base of the image receiving sheet include various papers, plastic films, rubber films and the like. Paper includes art paper, fine paper, coated paper, gravure paper, baryta paper, cellulose fiber paper, wallpaper, backing paper,
Examples include emulsion-impregnated paper, synthetic rubber latex-impregnated paper, and synthetic resin-containing paper. As plastic films, synthetic paper, polyolefin, polyvinyl chloride,
A single film or a laminate of a film such as polyethylene terephthalate, polystyrene, methacrylate, or polycarbonate is used.

Paper is preferred as the base material of the image receiving sheet because of its low cost. However, when the above-mentioned paper is used, unevenness on the surface of the paper may be picked up when pressed by a thermal head. In some cases, the image quality may be non-uniform, and it is particularly preferable to use a laminate having a cushion layer on the surface of the paper on which the receiving layer is formed as a base of the image receiving sheet from the viewpoint of improving the image quality. At this time, when the laminate is obtained by bonding, a known bonding agent such as an adhesive, a pressure-sensitive adhesive, or a release agent is used. Alternatively, a low-boiling liquid such as butane or pentane is used for polyvinylidene chloride,
An intermediate cushion layer containing hollow particles such as microspheres microencapsulated with a resin such as polyacrylonitrile may be provided. The thickness of the base of the image receiving sheet is suitably about 5 μm to 1 mm.

As the material used for the cushion layer,
Plastic films having air bubbles, for example, various known films such as polyester, polypropylene, vinyl chloride, polycarbonate, polyethylene, and acetate, and films having excellent cushioning properties such as rubber sheets without having air bubbles. No.

Above all, a bubble-containing plastic film such as a foamed polyester having a heat insulating effect is preferable from the viewpoint of sensitivity, and its density D is D / Do ≦ 0.7 (Do indicates the density of a plastic film of the same material containing no bubbles. Is more preferable. By using a bubble-containing plastic film that satisfies the above density D, a high image density can be obtained even in a low energy application section, and the effect is remarkable especially when applied to the n-fold mode method.

Further, it is preferable to provide a polyethylene layer on the back surface of the substrate of the image receiving sheet for sublimation transfer in the present invention for the purpose of preventing curling. As the method for forming the polyethylene layer, a known resin layer forming technique such as an extrusion lamination method can be used. If necessary, the polyethylene layer may contain an antistatic agent or a filler. As the antistatic agent to be used, any of conventionally known antistatic agents can be used. For example, anionic (phosphate ester type, There are various antistatic agents such as sulfonic acid type), cationic (quaternary ammonium salt type, tertiary amine type, etc.), nonionic (polyhydric alcohol ester type, amide type, fatty acid ester type, etc.), and amphoteric. . Examples of the filler include calcium carbonate, silica, titanium oxide, zinc oxide, and the like. By adding the filler, the storage stability of the image over time can be further improved, and blocking and set-off of the dye can be prevented. . Further, in order to improve the writability, the polyethylene layer may be matted. At this time, the thickness of the polyethylene layer is 0.1 to 5
About 0 μm is preferable.

The shape of the substrate is not particularly limited, and can be used in various sizes and various forms.
A card base can also be used. In this case, curling of the image receiving sheet does not occur even when heating is performed with high energy in the above-described heat treatment, so that high durability can be obtained. The card base is made of polyester, vinyl chloride, or the like, and may be provided with an IC memory, a magnetic layer, other printed matter, and the like. Further, a high image density can be obtained by using a card substrate on which a bubble-containing plastic film is laminated.

The image-receiving sheet for sublimation transfer of the present invention is particularly preferably one in which an over-layer having excellent heat resistance and lubricity is further laminated on the image-receiving layer. More specifically, a general image-receiving layer or the like contains a non-crosslinked thermoplastic resin for improving dyeing properties and, if necessary, a release agent such as silicone oil or silicone resin for preventing fusion with the ink layer. The added one is used. However, since the recording layer of the present invention also uses the speed difference mode method at the time of recording, the receiving layer or the over layer needs the above-mentioned heat resistance and lubricity.

In this case, with respect to the heat resistance, it is indispensable to improve the heat resistance of the image receiving layer and the over layer in order to prevent fusing and sticking at a speed difference at which shear stress is generated which is not present in constant velocity recording. However, in other words, the improvement in heat resistance impedes the diffusion of the dye in the image receiving layer and the over layer, and the dye in the layer is located near the surface compared to the image receiving layer of general constant-speed recording and the over layer. From the viewpoint of greatly improving the probability and reducing the above-mentioned inconvenience due to concerns about the decrease in durability, reheating differs from general constant-speed recording and is useful for improving defects caused by a speed difference.

As for the addition of lubricity, the releasability in general constant velocity recording is determined by the ink layer (dye layer) of the thermal transfer sheet.
Although essential for preventing fusion with the ink, the slippage between the ink layer and the image receiving layer during recording causes wrinkles on the ink ribbon (thermal sublimation transfer sheet), and as a result, Although performance is indispensable for speed difference recording due to inconveniences such as missing wrinkles, it is a performance that should not be contradictory to constant speed recording.

As described above, the image receiving layer and the over layer of the image receiving sheet suitable for the present invention are AST which cannot be an ordinary image receiving sheet for constant speed recording by adding heat resistance and lubricity.
An image receiving sheet surface and an aromatic polyamide film TX-1 (manufactured by Toray Industries, Ltd.) having a softening point of 200 ° C. or more were weighed at 200 g weight / 6 in a Haydon surface measuring instrument based on M.D 1894.
Superposed at 3.5 × 63.5mm ² , 75mm / m
The coefficient of kinetic friction μ at 100 ° C. when the TX-1 film is moved to “in” is preferably less than 0.45.

Examples of the lubricating substance used in the over layer include petroleum-based lubricating oils such as liquid paraffin, halogenated hydrocarbons, diester oils, synthetic lubricating oils such as silicone oil and fluorine silicone, and various modified silicone oils (epoxy-modified, Amino-modified, alkyl-modified, polyether-modified, etc.), silicone-based lubricating substances such as copolymers of organic compounds such as polyoxyalkylene glycol and silicone, and various fluorine-based surfactants such as silicone copolymers and fluoroalkyl compounds , Fluorinated lubricating substances such as low-polymerized trifluoroethylene chloride, waxes such as paraffin wax and polyethylene wax, higher aliphatic alcohols, higher aliphatic amides, higher fatty acid esters, higher fatty acid salts, molybdenum disulfide, etc. it can. These lubricating substances may be used alone or in combination of two or more.

In particular, when a silicone copolymer (resin obtained by polymerizing silicone by block or graft on a resin) is compared with a liquid lubricant, silicone chains are arranged on the surface irrespective of the degree of bleeding on the layer surface. It is possible to reduce the friction coefficient (μ value) without fail,
Good results for sticking. As the silicone copolymer, any resin obtained by polymerizing an acrylic resin, a polystyrene resin, a polynitrile resin, a polyamide resin, a polyurethane resin, a polyvinyl ether resin, or the like with silicone by block or graft may be used. Good are silicone graft copolymers. These lubricating substances are:
It may be a kind or a mixture of two or more kinds.

The above-mentioned lubricating substance can be used together with a silicone resin when forming an image by the n-fold mode method.
Due to the high heat resistance and releasability of the silicone resin and the lubricating effect of the lubricating substance, it is possible to obtain a good image without causing recording abnormality such as fusion, sticking or sheet breakage. . At this time, the thickness of the over layer is preferably about 0.05 to 10 μm.

Further, in the over layer, a silicone resin having a low dyeing property is used in the over layer in an amount of less than 85% by weight in order to increase the image density as well as the anti-fusing and sticking resistance as printing characteristics. It is preferred that Although silicone resin is excellent in release property (prevention of fusion), it has a low dyeing ability, which may cause a side effect of lowering the sensitivity of the receiving paper. In addition, poor storage stability of the dye remaining in the over layer after reheating of recording. Is concerned. In order to solve the above problems, the resin component of the silicone copolymer among the lubricants mixed with the silicone resin is preferably made of a resin having a dyeing property. In other words, by including a resin component capable of dyeing the dye, the stability of the dye remaining in the over layer during storage is increased, and the dye diffusion from the ink layer is smoothly performed due to the increase in compatibility with the dye in the over layer. Progressing results in increased sensitivity.

The dyeable resin is evaluated and determined by the following method. Synthetic paper YUPO FPG # 95 (manufactured by Oji Yuka Co., Ltd.) was used as a substrate base, and a modified silicone solution containing 30% of resin solids in each of the resin solutions studied dissolved in a volatile solvent in an amount of 5 to 20% by weight on the substrate base. Oil SF8411 / SF84
A liquid containing 21 = 1/1 (manufactured by Toray Silicone Co., Ltd.) is applied to a dry film thickness of about 10 μm, dried at 70 ° C. for 1 minute, and then dried at room temperature for 1 day or more. Next, the image receiving paper formed above and the Mitsubishi color video processor SCT
-A color sheet for CP200 and a cyan ribbon are superimposed and recorded at 2.00 mJ / dot using a thermal head KMT-85-6MPD4 (manufactured by Kyocera) having a resolution of 6 dots / mm and an average resistance of 542 Ω. The recording density is evaluated by a reflection densitometer RD-918. As a result, those having a recording density of 1.2 or less are designated as low-dyeing resins, and the others are designated as dyeable resins.

As a result of the evaluation as described above, as the binder resin of the silicone graft copolymer used in the over layer, a polyamide resin, a polyolefin resin, an epoxy resin, a polybutyral resin, a polyurethane resin and the like can be mentioned. , As those that are commercially available,
Dialomer SP302S, SP2105, SP71
1, SP712 (manufactured by Dainichi Seika) and the like.

Providing the over-layer with dyeing properties prevents deterioration of image quality due to bleeding of the dye on the surface of the image-receiving layer and deterioration of image quality such as image blur due to dye contamination during long-term storage after image formation. It becomes possible. Further, by making the thickness of the over layer 2 μm or less, the dye at the time of printing can be more diffused into the highly dyeable receiving layer, so that the density can be increased, and the dye in the over layer can be formed. By reducing the amount, it is possible to prevent a decrease in image quality during longer-term storage.

When a silicone graft copolymer is used in combination with the overlayer, a silicone oil may be contained in order to further improve anti-fusing and anti-sticking properties. And fluorine-modified silicone oil, amino-modified silicone oil, carboxy-modified silicone oil, polyether-modified silicone oil and the like. Of these, non-modified silicone oil and epoxy-modified silicone oil are particularly preferred.

The unmodified silicone oil is a silicone oil which has not been modified at all, such as dimethyl silicone oil, methylphenyl silicone oil and methyl hydrogen silicone oil. Commercially available products include KF96L, KF96, and KF96.
H, KF69, KF92, KF961, KF50, KF
54, KF965, KF968, KF56 (all manufactured by Shin-Etsu Chemical Co., Ltd.), SH200, BY16-140, SH51
0, SH550, SH710 and SH1107 (all manufactured by Toray Silicone Co., Ltd.).

The above-mentioned epoxy-modified silicone oil is
Silicone oils having epoxy groups introduced at both ends or side chains of a dimethyl silicone skeleton and commercially available are KF100T, KF101, KF102,
KF103 (above, Shin-Etsu Chemical bleeds in a large amount, so blocking occurs. When the image is stored in a file or the like after image formation, sticking occurs.

When the silicone oil is added to the overlayer-forming solution and applied to the surface of the receptor layer, the overlayer-forming solution contains a solvent compatible with the silicone oil in an amount of 25% by weight or more of the total solvent of the overlayer-forming solution. It is better to use If the silicone oil is insoluble and cloudy in the over-layer forming liquid, bleeding occurs during the application of the over-layer forming liquid, resulting in poor film formation. The solvent of the overlayer forming solution may be formed of only one solvent soluble in silicone oil, but contains at least 25% by weight or more of a solvent compatible with silicone oil in order to prevent film formation failure and dissolve the resin used. Any solvent configuration may be used.

The silicone resin used in the overlayer of the present invention is a three-dimensionally crosslinked silicon polymer having a siloxane bond as a main chain, and any known one can be used. For example, SR2406, SR2410, SR242
0, SR2416, SR2405, SR2411 (all manufactured by Toray Silicone Co., Ltd.), KR220, KR230,
KR255, KR280, KR285, KR211, K
R212, KR214, and KR216 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. If necessary, a catalyst such as a metal salt of an organic carboxylic acid (such as lead, iron, or tin) or an amine may be used to promote the crosslinking reaction. .

As the other over layer, an image is transferred onto the image receiving layer, and then a film is placed on a part or all of the image receiving layer and laminated with reheating. It is also possible.

The light resistance can be further improved by including an ultraviolet absorbent in the above-mentioned over layer. As the ultraviolet absorber used in the present invention, known ultraviolet absorbers such as benzophenone type, benzotriazole type, cyanoacrylate type, salicylate type and oxalic anilide type can be used. When a low molecular weight type ultraviolet absorber is used, the melting point is preferably 60 ° C. or higher, and when the melting point is lower than 60 ° C., the image receiving sheet for sublimation transfer and the thermal transfer sheet may be fused during image formation. And uneven image density may occur. In addition, a known polymer type ultraviolet absorber can also be used.

The addition amount of these ultraviolet absorbers is preferably 1 to 50% by weight based on the total weight of the resin in the over layer, and if less than 1% by weight, the effect on light resistance is insufficient. When the amount exceeds 50% by weight, the light resistance is sufficiently effective, but the yellow color of the ultraviolet absorbent itself causes the image receiving sheet to turn yellow, and the whiteness is reduced, and the image quality is reduced due to the bleeding of the ultraviolet absorbent.

Further, known additives such as an antioxidant and a light stabilizer can be added to the above-mentioned over layer, if necessary. Further, it is preferable to provide a polyethylene layer on the back surface of the substrate of the image receiving sheet for sublimation transfer in the invention for the purpose of preventing curling. As a method for forming the polyethylene layer, a known resin layer forming technique such as an extrusion lamination method can be used.

As the heat-sensitive sublimation transfer sheet used in the sublimation type thermal transfer recording method of the present invention, conventionally known ones can be used as long as they have at least a sublimation dye layer on a substrate. When applied to a so-called n-times mode method in which the recording is performed with the former traveling speed set to n times (n> 1) the latter traveling speed in the superposed state, the method is proposed in JP-A-2-586. A transfer sheet in which a dye supply layer having a high dye concentration and a transfer contributing layer having a low dye concentration are laminated on a substrate is preferable.

As the sublimable dye used in the dye layer (dye supply layer, transfer contributing layer) of the dye transfer sheet, a sublimable dye known in the art is used. I. Disperse Yellow 1,3,8,9,16,41,54,6
0, 77, 116 and the like. I. Disperse Red 1,4,6,11,15,17,55,59,60,7
3,83 and the like. I. Disperse Blue 3,1
4,19,26,56,60,64,72,99,10
8, Solvent Yellow 23, 25, 27, etc .; Solvent Blue 36, 83, 105, etc., and these dyes may be used alone or in combination.

The dye layer is generally formed by dissolving or dispersing the above-described sublimable dye in a binder resin, and a thermoplastic or thermosetting resin is used as the binder resin. Is polyvinyl chloride, polyvinyl acetate, polyamide, polyethylene, polycarbonate, polystyrene, polypropylene, acrylic resin,
Examples include phenolic resin, polyester, polyurethane, epoxy resin, silicone resin, butyral resin, polyvinyl alcohol, and cellulose resin. One of these resins can be used, or a mixture of several resins or a copolymer thereof may be used.

It is preferable that a lubricant is added to the transfer contributing layer of the dye transfer sheet or the surface layer provided as necessary. Examples of lubricants include petroleum lubricating oils such as liquid paraffin, halogenated hydrocarbons, diester oils, silicone oils, synthetic lubricating oils such as fluorosilicone, and various modified silicone oils (epoxy-modified, amino-modified, alkyl-modified,
Silicone-based lubricating substances such as copolymers of organic compounds such as polyoxyalkylene glycols and silicone, silicone-based lubricating substances such as fluoroalkyl compounds, and fluorine-based surfactants such as low-polymerized trifluoroethylene chloride. Lubricating substances, waxes such as paraffin wax and polyethylene wax, higher fatty acids, higher fatty alcohols, higher fatty amides, higher fatty acid esters, higher fatty acid salts, molybdenum disulfide and the like can be used. These lubricants may be used alone or in combination of two or more.

In the present invention, the dye transferred to the image receiving sheet is pushed into the dye receiving layer by subjecting the image receiving sheet for sublimation transfer on which an image is formed to a heat treatment.
Other durability improvements such as storage stability and plasticizer resistance, and further improvements in light resistance can be achieved.

As the heat treatment method used in the present invention, a known method can be used. For example, a heat roll, a hot stamp, a thermal head, a laser beam, an infrared lamp, a xenon lamp, a hot pen, and the like can be used. Among them, the use of a thermal head in particular does not require an additional heating device, and reduces cost. It is preferable from the viewpoint. These heat treatments may be performed once, but may be performed two or more times as desired.

When a thermal head is used for the above heat treatment, the heat treatment may be performed via a heat transfer sheet having a region containing no dye or another heat treatment sheet to protect the thermal head and the like. preferable.
Above all, it is preferable to continuously provide a dye layer and a region containing no dye on the thermal transfer sheet because the problem of preparing another sheet for heat treatment is eliminated, and it is particularly preferable that yellow, magenta, cyan and It is preferable to provide a region containing no dye on the thermal transfer sheet having an area formed by applying black as necessary. The area not containing the dye can be heated even if it is shorter than the image area to be heated.

A heat transfer sheet having a dye-free region or another heat treatment sheet used in the heat treatment is used in order to favorably perform heat treatment by the n-fold mode method.
The uppermost layer is preferably a low-dyeing resin layer. Examples of the resin used in the low-dyeing resin layer include, for example, an aromatic polyester resin, a styrene butadiene resin, a polyvinyl acetate resin, a polyamide resin, and a particularly preferred resin, a methacrylate resin or a copolymer thereof,
Examples include a styrene-maleic acid ester copolymer, a polyimide resin, a silicone resin or a copolymer thereof, a styrene acrylonitrile resin, and a polysulfone resin.

Further, on the back surface of the heat transfer sheet or the other heat treatment sheet having a region containing no dye used in the heat treatment, a heat-resistant lubricating layer is formed so that the heat treatment by the n-fold mode method can be performed well. Can also be provided.

[0071]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. All parts are parts by weight.

(Preparation of Transfer Sheet I) An intermediate adhesive layer forming solution was applied using a wire bar to the surface of a 6 μm thick aromatic polyamide film having a 1 μm thick silicone resin heat-resistant layer on the back surface, and heated at 120 ° C. At 90 ° C. for 24 hours.
A μm intermediate adhesive layer was formed. Next, a dye supply layer having a thickness of 3 μm, a transfer contributing layer having a thickness of 1 μm, and a low-dyeing resin layer having a thickness of 1 μm were sequentially coated with a wire bar, and dried at 100 ° C. for 90 seconds and aged at 60 ° C. for 24 hours. By laminating, a dye transfer sheet I was prepared.

[Intermediate adhesive layer forming solution] Polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) 10 parts Isocyanate compound 10 parts (trade name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) Toluene 95 parts Methyl ethyl ketone 95 parts

[Dye Supply Layer Forming Solution] Polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) 10 parts Isocyanate compound 5 parts (trade name: Coronate L, manufactured by Nippon Polyuren Co.) Sublimable dye (trade name) : R-1, manufactured by Nippon Kayaku Co., Ltd.) 25 parts Ethanol 180 parts n-butanol 10 parts

[Transfer Contributing Layer Forming Solution] Polyvinyl butyral resin 10 parts (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) Isocyanate compound 5 parts (trade name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) Sublimable dye (trade name) : R-1, Nippon Kayaku Co., Ltd.) 10 parts Toluene 95 parts Methyl ethyl ketone 95 parts

[Low Dyeing Layer Forming Solution] Styrene-maleic acid copolymer 10 parts (trade name: Suprapearl AP30, manufactured by BASF) Liquid A ^* 12 parts Tetrahydrofuran 20 parts Methyl ethyl ketone 95 parts * Liquid A: 15 g of dimethylmethoxysilane And 9 g of methyltrimethoxysilane in a mixed solvent of 12 g of toluene and 12 g of methyl ethyl ketone, and hydrolyzed for 3 hours by adding 13 ml of 3% sulfuric acid.

(Preparation of Image Receiving Sheet I)
31, the liquid X for forming a dye receiving layer of Comparative Examples 1 to 4) was
And dried at 80 ° C. to form a dye receiving layer having a thickness of 5 μm. Then, on this dye receiving layer, the following formulas (Examples 1 to 31 and Comparative Examples 1 to 4) Liquid Z is applied to a thickness of 1.0 μm, dried at 100 ° C., and then subjected to an aging treatment at 80 ° C. for 16 hours to form a 1.0 μm thick overlayer, which is used for sublimation transfer. An image receiving sheet I was prepared.

[Recording Conditions] A recording evaluation test was performed under the following recording conditions by superposing the dye layer of the dye transfer sheet I and the image receiving sheet I so as to be in contact with each other. Applied gravity 0.16 W / dot Thermal head 12 dot / mm (running speed of image receiving sheet) / (running speed of transfer sheet)
= 12 applied energy 0.64 mJ / dot

Example 1 Y: Synthetic paper (trade name: Yupo, manufactured by Oji Yuka Synthetic Paper Co., Ltd.) [X: Liquid for forming dye receiving layer] 9.4 parts of vinyl chloride / vinyl acetate / vinyl alcohol copolymer ( Trade name: Denka vinyl # 1000GKT, manufactured by Denki Kagaku Kogyo) 3.2 parts of isocyanate compound (trade name: D140N, manufactured by Takeda Pharmaceutical Co., Ltd.) Toluene 21.4 parts Methyl ethyl ketone 64.3 parts [Z: Overlayer forming liquid 1 9.25 parts of silicone resin (trade name: SR2411, manufactured by Toray Silicone Co., Ltd.) 14.80 parts of silicone graft resin (trade name: SP712, manufactured by Dainichi Seika Co., Ltd.) 0.02 parts of ultraviolet absorber (trade name: Sumisorb 100 , Manufactured by Sumitomo Chemical Co., Ltd.) Epoxy-modified silicone oil 0.37 parts (trade name: SF8411, manufactured by Toray Silicone Co., Ltd.) Creating the image receiving sheet Le 37.96 parts Toluene 37.96 parts The above formulation. The recording evaluation test was performed, and the results are shown in Table 2.

Example 2 An image receiving sheet was prepared in the same manner as in Example 1 except that the ultraviolet absorber was changed from 0.02 part to 0.74 part in the overlayer forming solution of Example 1. The recording evaluation test was performed, and the results are shown in Table 2.

Example 3 An image receiving sheet was prepared in the same manner as in Example 1 except that the ultraviolet absorber in the overlayer forming solution of Example 1 was changed from 0.02 parts to 2.22 parts. The recording evaluation test was performed, and the results are shown in Table 2.

Example 4 An image obtained in the same manner as in Example 1 was overlaid so that the following low-dyeing resin layer of the heat-treating sheet I was in contact with each other, and heat-treated under the following conditions. The recording evaluation test was performed, and the results are shown in Table 1. Applied power 0.16 W / dot Thermal head 12 dot / mm (traveling speed of image receiving sheet) / (traveling speed of heat treatment sheet) = 1 Applied energy 0.50 mJ / dot [Preparation of heat treatment sheet I] Thickness 1 μm The intermediate adhesive layer forming liquid was applied to the surface of an aromatic polyamide film having a thickness of 6 μm having a silicone resin heat-resistant layer on the back surface using a wire bar, and dried at 120 ° C. for 90 seconds.
Aging treatment is performed at 0 ° C. for 24 hours, and the thickness is 1 μm.
Was formed. Then, the above-mentioned low-dyeing resin layer forming liquid was applied to the intermediate adhesive layer by wire bar application, and
After drying at 00 ° C. for 90 seconds and aging at 60 ° C. for 24 hours, a 1 μm-thick low-dye resin layer was laminated to prepare a sheet for heat treatment. The recording evaluation test was performed, and the results are shown in Table 1.

Embodiment 5 In Embodiment 4, the applied energy of the heat treatment was set to 0.50.
The heat treatment was performed in the same manner as in Example 4, except that the mJ / dot was changed to 0.60 mJ / dot. The recording evaluation test was performed, and the results are shown in Table 1.

Example 6 A heat treatment was carried out in the same manner as in Example 4 except that the ratio of (running speed of image-receiving sheet) / (running speed of heat-treating sheet) was changed from 1 to 9 in Example 5. . The recording evaluation test was performed, and the results are shown in Table 1.

Example 7 A heat treatment was performed in the same manner as in Example 4 except that the ratio of (running speed of the image receiving sheet) / (running speed of the sheet for heat treatment) was changed to 12. The recording evaluation test was performed, and the results are shown in Table 1.

Example 8 In Example 7, the heating applied energy was set to 0.53 mJ /
A heat treatment was performed in the same manner as in Example 7 except that the temperature was changed to dot. The recording evaluation test was performed, and the results are shown in Table 1.

Example 9 In Example 7, the heating applied energy was changed to 0.60 mJ /
A heat treatment was performed in the same manner as in Example 7 except that the temperature was changed to dot. The recording evaluation test was performed, and the results are shown in Table 1.

Example 10 In Example 7, the heating applied energy was changed to 0.62 mJ /
A heat treatment was performed in the same manner as in Example 7 except that the temperature was changed to dot. The recording evaluation test was performed and the results are shown in Table 1.

Example 11 In Example 4, the applied energy of the heat treatment was set to 0.5.
Example 4 except that 0 mJ / dot was changed to 0.60 mJ / dot and the ratio of (running speed of image receiving sheet) / (running speed of heat treatment sheet) was changed from 1 to 18.
A heat treatment was performed in the same manner as described above. The recording evaluation test was performed, and the results are shown in Table 1.

Example 12 A heat treatment was performed in the same manner as in Example 9, except that the image obtained in Example 2 was used.
The recording evaluation result test was conducted and the results are shown in Table 1.

Example 13 An image receiving sheet was prepared in the same manner as in Example 1 except that X was changed to coated paper (trade name: OK Coat, manufactured by Oji Yuka Co., Ltd.). Done. Table 2 shows the results.

Example 14 In Example 1, X was coated on coated paper (trade name: OK Coat, manufactured by Oji Yuka Co., Ltd.) on a bubble-containing polypropylene (trade name: Toyopearl ST, manufactured by Toyobo Co., Ltd. [Density: D / Do = 0] .74])
An image receiving sheet was prepared in the same manner as in Example 1 except that the layer was provided with a layer (thickness: 50 μm), and a recording evaluation result test was performed. Table 2 shows the results.

Example 15 In Example 1, X was coated on coated paper (trade name: OK Coat, manufactured by Oji Yuka Co., Ltd.) on a bubble-containing polypropylene (trade name: YP).
56, an image-receiving sheet was prepared in the same manner as in Example 1 except that the laminate was a laminate having a [density: D / Do = 0.66] layer (thickness: 50 μm) manufactured by Toray Co., Ltd. A record evaluation result test was performed. Table 2 shows the results.

Example 16 In Example 1, X was coated on a coated paper (trade name: OK Coat, manufactured by Oji Yuka Co., Ltd.) on a bubble-containing polyester (trade name: E60).
Toray [density: D / Do = 0.62]) layer (thickness 5
An image receiving sheet was prepared in the same manner as in Example 2 except that the thickness of the image receiving sheet was changed to that provided with 0 μm), and a recording evaluation result test was performed. Table 2 shows the results.

Example 17 An image receiving sheet was prepared in the same manner as in Example 2 except that a polyethylene layer was provided on the back surface of the substrate used in Example 16.
A record evaluation test was performed. Table 2 shows the results.

Example 18 The cell-containing polyester used in Example 16 (trade name:
An image receiving sheet was prepared in the same manner as in Example 2 except that a card base obtained by laminating E60 (manufactured by Toray Industries Co., Ltd.) on a white PET plate having a thickness of 750 μm was used, and a recording evaluation result test was performed. Table 2 shows the results.

Comparative Example 1 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution of Example 1 was changed as follows, and a recording evaluation test was performed. The results are shown in Table 2. [Liquid for forming over layer] Silicone resin (trade name: SR2411, manufactured by Toray Silicone Co., Ltd.) 9.25 parts Polyvinyl butyral (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) 1.85 parts Isopropyl alcohol 88.90 parts

Comparative Example 2 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution of Example 1 was changed as follows, and a recording evaluation test was performed. Table 2 shows the results. [Liquid for forming over layer] Polyvinyl butyral (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) 3.70 parts Epoxy-modified silicone oil (trade name: SF8411, manufactured by Toray Silicone Co., Ltd.) 0.37 parts Methyl ethyl ketone 48.15 parts Toluene 48.15 parts

Example 19 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution of Example 1 was changed as follows, and a recording evaluation test was performed in the same manner as in Example 1. Table 2 shows the evaluation results. [Liquid for forming overlayer] Silicone resin (trade name: SR2411, manufactured by Toray Silicone Co., Ltd.) 9.25 parts Silicone graft resin (trade name: SP712, manufactured by Dainichi Seika Co., Ltd.) 14.80 parts Epoxy-modified silicone oil 0.37 Parts (trade name: SF8411, manufactured by Toray Silicone Co., Ltd.) Isopropyl alcohol 37.97 parts Toluene 37.97 parts

Example 20 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution in Example 1 was changed as follows, and the thickness of the overlayer was changed to 3 μm. An evaluation test was performed. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [trade name: SR2411 (resin solid content 20% solvent, toluene), manufactured by Toray Silicone Co., Ltd.] 18.5 parts Alcohol-modified silicone oil (trade name: SF8427, manufactured by Toray Silicone Co., Ltd.) 37 parts Isopropyl alcohol 81.5 parts

Example 21 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution in Example 1 was changed as follows, and the thickness of the overlayer was changed to 3 μm. An evaluation test was performed. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [trade name: SR2411 (resin solid content 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 16.65 parts acrylic silicone block copolymer [trade name: LDL500 (resin solid content 30%) Solvent isopropyl alcohol) manufactured by Natco, dyeing concentration 1.02] 0.37 parts Isopropyl alcohol 85.5 parts

Example 22 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution in Example 1 was changed as follows, and the thickness of the overlayer was changed to 3 μm. An evaluation test was performed. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [Product name: SR2411, (Toluene resin 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 18.5 parts Acrylic silicone graft resin [Product name: US350 (Resin solid content 30% solvent) Methyl ethyl ketone) Toa Gosei Co., Ltd., dyeing density 1.05] 2.47 parts Methyl ethyl ketone 42.75 parts Toluene 42.75 parts

Example 23 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution of Example 1 was changed as follows, and the thickness of the overlayer was changed to 3 μm. An evaluation test was performed. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [Product name: SR2411 (Toluene resin 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 9.25 parts Acrylic silicone graft resin [Product name: US350 (Resin solid content 30% solvent) Methyl ethyl ketone, manufactured by Toa Gosei Co., Ltd., dyeing density 1.05] 6.17 parts Methyl ethyl ketone 42.75 parts Toluene 42.75 parts

Example 24 An image receiving sheet was prepared in the same manner as in Example 1 except that the solution for forming the overlayer in Example 1 was changed as follows, and the same recording evaluation test as in Example 1 was performed. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [trade name: SR2411 (resin solid content 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 9.25 parts Silicone graft resin [trade name: SP712 (resin solid content 12.5% solvent) Methyl ethyl ketone) DAINICHI SEIKA CORPORATION, dyeing concentration 1.50] 14.8 parts Isopropyl alcohol 75.95 parts

Example 25 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution in Example 1 was changed as follows, and a recording evaluation test was performed in the same manner as in Example 1. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [trade name: SR2411 (resin solid content 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 9.25 parts Silicone graft resin [trade name: SP712 (resin solid content 12.5% solvent) Methyl ethyl ketone) Dye concentration: 1.50], 14.8 parts Amino-modified silicone oil (trade name: SF8417, manufactured by Toray Silicone Co.) 0.07 parts Isopropyl alcohol 75.95 parts

Example 26 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution in Example 1 was changed as follows, and a recording evaluation test was performed in the same manner as in Example 1. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [trade name: SR2411 (resin solid content 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 9.25 parts Silicone graft resin [trade name: SP712 (resin solid content 12.5% solvent) Methyl ethyl ketone) Dye concentration: 1.50 manufactured by Dainichi Seika Co., Ltd. 14.8 parts Epoxy-modified silicone oil (trade name: SF8411, manufactured by Toray Silicone Co., Ltd.) 0.07 parts Isopropyl alcohol 75.95 parts

Example 27 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution in Example 1 was changed as described below, and the same recording evaluation test as in Example 1 was performed. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [trade name: SR2411 (resin solid content 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 9.25 parts Silicone graft resin [trade name: SP712 (resin solid content 12.5% solvent) Methyl ethyl ketone) DAINICHI SEIKA CORPORATION, dyeing concentration 1.50] 14.8 parts Unmodified silicone oil (trade name: SH200, manufactured by Toray Silicone Co., Ltd.) 2.22 parts Isopropyl alcohol 75.95 parts

Example 28 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution of Example 1 was changed as described below, and the same recording evaluation test as in Example 1 was performed. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [trade name: SR2411 (resin solid content 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 9.25 parts Silicone graft resin [trade name: SP712 (resin solid content 12.5% solvent) Methyl ethyl ketone) Dye concentration: 1.50 manufactured by Dainichi Seika Co., Ltd. 14.8 parts Epoxy-modified silicone oil (trade name: SF8411, manufactured by Toray Silicone Co., Ltd.) 0.11 part Isopropyl alcohol 75.95 parts

Example 29 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution of Example 1 was changed as follows, and the same recording evaluation test as in Example 1 was performed. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [trade name: SR2411 (resin solid content 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 9.25 parts Silicone graft resin [trade name: SP712 (resin solid content 12.5% solvent) Methyl ethyl ketone) DAINICHI SEIKA CORPORATION, dyeing concentration 1.50] 14.8 parts Unmodified silicone oil (trade name: SH200, manufactured by Toray Silicone Co., Ltd.) 0.95 parts Isopropyl alcohol 75.95 parts

Example 30 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution of Example 1 was changed as follows, and the same recording evaluation test as in Example 1 was performed. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [trade name: SR2411 (resin solid content 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 9.25 parts Silicone graft resin [trade name: SP712 (resin solid content 12.5% solvent) Methyl ethyl ketone) Dye concentration: 1.50 manufactured by Dainichi Seika Co., Ltd. 14.8 parts Epoxy-modified silicone oil (trade name: SF8411, manufactured by Toray Silicone Co., Ltd.) 0.37 parts Isopropyl alcohol 75.95 parts

Example 31 An image receiving sheet was prepared in the same manner as in Example 1 except that the overlayer forming solution in Example 1 was changed as follows, and a recording evaluation test was performed in the same manner as in Example 1. Table 2 shows the results. [Liquid for forming over layer] Silicone resin [trade name: SR2411 (resin solid content 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 9.25 parts Silicone graft resin [trade name: SP712 (resin solid content 12.5% solvent) Methyl ethyl ketone) Dye concentration: 1.50 manufactured by Dainichi Seika Co., Ltd. 14.80 parts Epoxy-modified silicone oil (trade name: SF8411, manufactured by Toray Silicone Co., Ltd.) 0.37 parts Isopropyl alcohol 37.97 parts Toluene 37.97 parts

Comparative Example 3 An image receiving sheet for sublimation transfer was prepared in the same manner as in Example 1 except that the following overlayer forming solution was used in place of the overlayer forming solution in Example 1. The recording evaluation test was performed, and the results are shown in Table 2. [Liquid for forming over layer] Polyvinyl butyral (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) 3.7 parts Methyl ethyl ketone 48.15 parts Toluene 48.15 parts

Comparative Example 4 An image receiving sheet for sublimation transfer was prepared in the same manner as in Example 1, except that the following overlayer forming solution was used in place of the overlayer forming solution in Example 1. The recording evaluation test was performed, and the results are shown in Table 2. [Liquid for forming over layer] Silicone resin [Product name: SR2411 (resin solid content 20% solvent toluene), manufactured by Toray Silicone Co., Ltd.] 18.5 parts Isopropyl alcohol 81.5 parts

Comparative Example 5 A dye receiving layer solution and an over layer solution were sequentially coated on a 150 μm-thick synthetic paper (trade name: Yupo G-150; manufactured by Oji Yuka Synthetic Paper Co., Ltd.) by a coating method. After drying, a dye receiving layer having a thickness of 5 μm was formed on the synthetic paper, and an overlayer having a thickness of 1 μm was formed on the image receiving layer to form an image receiving sheet.
A recording evaluation test was performed under the same conditions as in Example 1, and the results are shown in Table 2. (Receiving layer liquid) Vinyl chloride-isobutyl vinyl ether copolymer (BASF Co., Ltd., Laroflex MP25) 9 parts Trimellitic acid alkyl ester (Asahi Denka Kogyo Co., Ltd., Adekizer C79) 1 part Methyl ethyl ketone 80 parts Cyclohexane 10 parts (Over Layer solution) Polyvinyl chloride (TK600, Shin-Etsu Chemical Co., Ltd.) 9.5 parts Polyester modified silicone resin (X-24-8300, Shin-Etsu Silicone Co., Ltd.) 0.5 parts Methyl ethyl ketone 80 parts Cyclohexanone 10 parts

(Preparation of Transfer Sheet II) A dye supply layer forming solution was applied using a wire bar to the surface of a 6 μm thick PET film having a 1 μm thick silicone resin heat-resistant layer on the back surface, and heated at 80 ° C. for 90 seconds. Is dried to a thickness of 1.2
A dye transfer layer II was formed by laminating a μm dye supply layer. [Dye supply layer forming liquid] Polyvinyl butyral resin 10 parts (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) Sublimable dye (trade name: R-1, manufactured by Nippon Kayaku Co., Ltd.) 10 parts Toluene 95 parts Methyl ethyl ketone 95 parts

(Preparation of Image Receiving Sheet II) The following (Example 3)
2. The dye receiving layer forming liquid X ′ of Comparative Examples 6 and 7) is applied on a substrate Y ′, and dried at 80 ° C. to form a dye receiving layer having a thickness of 5 μm. An overlayer forming liquid Z having the following formulation was applied and dried at 100 ° C. to form an overlayer having a thickness of 1.0 μm. Thus, an image receiving sheet II for sublimation transfer was prepared.

[Recording conditions] The dye layers of the above dye transfer sheet II were overlapped so that the image receiving sheet II was in contact therewith, and a recording evaluation test was performed under the following recording conditions. Applied voltage 0.13W / dot Thermal head 12dot / mm (running speed of image receiving sheet) / (running speed of transfer sheet)
= 1 applied energy 0.41 mJ / dot

Example 32 Y ': Synthetic paper (trade name: YUPO, manufactured by Oji Yuka Synthetic Paper Co., Ltd.) [X': Liquid for forming dye-receiving layer] Vinyl chloride / vinyl acetate / vinyl alcohol copolymer 9.4 Part (trade name: Denka Vinyl # 1000GKT, manufactured by Denki Kagaku Kogyo) Toluene 21.4 parts Methyl ethyl ketone 64.3 parts [Z ': Overlayer forming liquid 1] Silicone graft resin (trade name: SP712, manufactured by Dainichi Seika Co., Ltd.) 14.80 parts UV absorber (trade name: Sumisorb 100, manufactured by Sumitomo Chemical Co., Ltd.) 0.02 parts Isopropyl alcohol 37.96 parts Toluene 37.96 parts The obtained image on the image receiving sheet and the above-mentioned heat treatment The sheet I was overlaid so as to be in contact with the low-dyeing resin layer, and heat-treated under the following conditions. A recording evaluation test was performed, and the results are shown in Table 1. Applied power 0.16 W / dot Thermal head 12 dot / mm (travel speed of image receiving sheet) / (travel speed of heat treatment sheet) = 1 Applied energy 0.37 mJ / dot

Comparative Example 6 In Example 32, the applied energy of reheating was 0.50.
Recording and reheating were performed in exactly the same manner as in Example 32 except that mJ / dot was used. The recording evaluation test was performed, and the results are shown in Table 1.

Comparative Example 7 In Example 32, the energy applied for reheating was 0.25.
Recording and reheating were performed in exactly the same manner as in Example 32 except that mJ / dot was used. A recording evaluation test was performed, and the results are shown in Table 1.

(Evaluation Test) Table 1 shows the image evaluation of the above Examples and Comparative Examples with respect to the heat treatment by a thermal head based on the following evaluation method, and shows that the kinetic friction coefficient μ at 100 ° C. is less than 0.45. Table 2 shows the image evaluation of the sheet.

[Evaluation of Image Density] Macbeth reflection densitometer RD
Measured by -918.

[Evaluation of fusion and sticking]
= 12 Image samples obtained under the recording conditions were visually evaluated. ：: No fusion and sticking △: Partial fusion and sticking ×: Fusion and sticking all over

[Evaluation of Light Resistance] An image sample having an image density of 1.0 was irradiated with a xenon fade meter at 150,000 lux for 72 hours, and the image density remaining ratio was measured. Image density residual rate (%) = [image density after irradiation / image density before irradiation] × 100

[Evaluation of plasticizer resistance] Three sheets of polymer wrap manufactured by Shin-Etsu Polymer Co., Ltd. were superimposed on the recording surface of an image sample having an image density of 1.0, and a 5 kg weight / B5 plate (=
(182 × 257 cm ² ), and the image density residual ratio after 24 hours at 40 ° C. was measured. Residual image density (%) = [Image density after test / Image density before test] × 100 ◎: Residual rate of image density is 90% or more ○: Residual rate of image density is 75% or more and less than 90% △: Residual image density Ratio: 60% or more and less than 75% ×: Image density residual ratio less than 60%

[Evaluation of Storage Stability] An image sample having an image density of 1.0 was stored at 60 ° C. in a dark place for 30 days, and the residual ratio of the image density was measured. Image density residual rate (%) = [Image density after storage / Image density before storage] × 100 ：: Image density residual rate is 90% or more ：: Image density residual rate is 75% or more and less than 90% Δ: Image density residual Ratio: 60% or more and less than 75% ×: Image density residual ratio less than 60%

[Evaluation of Glossiness] PG-3 manufactured by Nippon Denshoku Industries Co., Ltd.
The 60 ° specular gloss was measured by a gloss meter. ：: 60% or more △: 45% or more, less than 60% ×: less than 45%

[Evaluation Method of Blocking Resistance] A PET film was superimposed on an image receiving sheet and 3 kg weight / B5 plate (= 18)
2 × 257 cm ² ) and a 65% R at 22 ° C.
The adhesive state after being left in the H atmosphere for 24 hours was evaluated.

[0129]

[Table 1]

[0130]

[Table 2]

As is clear from the description of the examples, the image receiving sheet for sublimation transfer and the sublimation type thermal transfer recording method of the present invention have problems such as fusing and sheet breakage during recording even in image formation using the n-fold mode method. Thus, it is possible to obtain a normal printed image without defects, and to obtain a high-density image without deterioration in image quality during long-term storage of the image.

[0132]

As described above, the image-receiving sheet for sublimation transfer of the present invention can obtain a normal printed image without problems such as fusing and sheet breakage during recording.
It is possible to prevent a decrease in image quality during long-term storage of an image. This is particularly effective in image formation using the n-times mode recording method.

According to the first and second aspects of the present invention, the heat treatment is performed by using a thermal head through a heat-sensitive sublimation transfer sheet having a dye-free area or another heat treatment sheet. By setting Ei> Eb with respect to the energy Eb and the applied energy Ei at the time of image formation, no special device is required, and light resistance, storage stability,
An image having excellent durability of plasticizer resistance, good image gloss without burning the image receiving sheet, and no abnormality in the reheating area of the heating sheet or the heat-sensitive sublimation transfer sheet can be obtained.

According to the third and fourth aspects of the present invention, the heat treatment is performed by the n-times mode method, and the length b of the heated area of the heat-sensitive sublimation transfer sheet having the area containing no dye is determined by the dye area of the heat transfer sheet. By setting b ≦ i with respect to the length i, an inexpensive, highly glossy and highly durable image can be obtained.

In the image-receiving sheet for sublimation transfer according to claim 5, the surface of the dye-receiving layer conforms to ASTM D1894.
Kinetic friction coefficient μ at 0.4 ° C. is less than 0.45, and the over layer is composed of a silicone resin and a lubricating substance, so that high heat resistance, excellent releasability and lubricity are obtained, and the n-fold mode recording method Also, in the image formation using, a normal printed image can be obtained without problems such as fusion, sticking, and sheet breakage.

In the image receiving sheet for sublimation transfer according to the sixth aspect of the present invention, the lubricating substance of the over layer is made of a silicone graft copolymer, so that even more excellent lubricity can be obtained even in image formation using the n-times mode recording method. A normal printed image can be obtained without problems such as adhesion and sheet breakage.

In the image receiving sheet for sublimation transfer according to the seventh aspect, by setting the content of the silicone resin in the overlayer to less than 85%, the dyeing property of the dye can be enhanced and a high image density can be obtained.

In the image receiving sheet for sublimation transfer according to the eighth aspect, by setting the thickness of the over layer to 2 μm or less, the amount of dye diffusion into the receiving layer can be increased, and a high image density can be obtained, and a long-term image can be obtained. Quality deterioration can be prevented.

In the image receiving sheet for sublimation transfer according to the ninth aspect, by using a silicone graft copolymer having a dyeing resin as a binder as a lubricating substance for the overlayer, the dyeing property of the dye is enhanced and a high image density is obtained. And a long-term reduction in image quality can be prevented.

In the image-receiving sheet for sublimation transfer according to any one of claims 10 to 13, the silicone oil is contained in the overlayer composed of a silicone resin and a silicone graft copolymer, and further, among the silicone oils, epoxy-modified or unmodified silicone. By containing the oil, even in image formation using the n-times mode recording method, it is excellent in anti-fusing and anti-sticking properties, and it is possible to obtain a normal printed image even with a high n-fold number. In addition, the amount of addition is preferably from 3 to 50%, more preferably from 5 to 15, from the influence of blocking properties and the like.

In the image receiving sheet for sublimation transfer according to the fourteenth aspect,
When silicone oil is contained in the overlayer composed of a silicone resin and a silicone graft copolymer, a solvent compatible with the silicone oil is contained as a solvent of the overlayer forming solution in a proportion of at least 25% of the total solvent of the overlayer forming solution. By stacking the layers, repelling of the silicone oil can be prevented, and image unevenness can be eliminated.

According to the fifteenth and sixteenth aspects of the present invention, since the overlayer formed on the surface of the dye receiving layer is made of a silicone resin, a lubricating substance, and an ultraviolet absorber, it is possible to form an image using the n-fold mode method. It is possible to obtain a normal printed image excellent in light resistance without any minor problems such as fusing and sheet breakage during recording.

According to the seventeenth aspect of the present invention, an inexpensive and high-durability image with good image quality can be obtained by forming a laminate of paper and a cushion layer.

According to the eighteenth aspect of the present invention, the cushion layer is made of a bubble-containing plastic film, and the density D of the bubble-containing plastic film is D / Do ≦ 0.7 (D
o) indicates the density of a plastic film of the same material that does not contain air bubbles), so that an inexpensive, high-quality and high-density image can be obtained.

According to the nineteenth aspect, by providing a polyethylene layer on the back surface side of the substrate, an inexpensive and curl-free image can be obtained.

According to the twentieth aspect of the present invention, by using a card substrate as the substrate, a curl-free image having high image quality, high density and excellent durability can be obtained.

According to the twenty-first aspect, the uppermost layer of the heat transfer sheet having a region containing no dye or another heat treatment sheet is made of a low-dyeing resin layer, whereby n
Good heat treatment can be performed twice.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shinya Kawahara 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company, Ltd.

Claims (21)

[Claims] 1. A dye-receiving layer surface of a sublimation transfer image receiving sheet having at least a dye receiving layer on a substrate, and an ink layer surface of a heat-sensitive sublimation transfer sheet having at least one or more ink layers on a substrate. After forming an image on a sublimation transfer image-receiving sheet by heating from the substrate side of the heat-sensitive sublimation transfer sheet, the sublimation transfer image-receiving sheet is subjected to a thermal head, a heat-sensitive sublimation transfer sheet having a dye-free area or A sublimation type thermal transfer recording method in which heat treatment is performed via another heat treatment sheet, wherein the applied energy Eb of the heat treatment is Ei> Eb with respect to the applied energy Ei during image formation. Thermal transfer recording method. 2. An applied energy Eb of the heat treatment is larger than an applied energy Ei at the time of image formation by Ei> Eb ≧
2. The sublimation type thermal transfer recording method according to claim 1, wherein the sublimation type thermal transfer recording method is 0.8 Ei. 3. A dye-receiving layer surface of a sublimation transfer image receiving sheet having at least a dye receiving layer on a substrate and an ink layer surface of a heat-sensitive sublimation transfer sheet having at least one or more ink layers on a substrate. After an image is formed on a sublimation transfer image-receiving sheet by heating from the substrate side of a heat-sensitive sublimation transfer sheet, the sublimation transfer image-receiving sheet is subjected to a thermal head, a heat-sensitive sublimation transfer sheet having a dye-free area or In another sublimation heat transfer recording method in which a heat treatment is performed through another heat treatment sheet, the length of the heat-sublimation transfer sheet or another heat treatment sheet having a region containing no dye is greater than the length of the image region. A sublimation type thermal transfer recording method characterized by being short. 4. The dye-receiving layer surface of a sublimation transfer image receiving sheet having at least a dye receiving layer on a substrate and the ink layer surface of a heat-sensitive sublimation transfer sheet having at least one or more ink layers on a substrate. After forming an image on a sublimation transfer image-receiving sheet by heating from the substrate side of the heat-sensitive sublimation transfer sheet, the sublimation transfer image-receiving sheet is subjected to a thermal head, a heat-sensitive sublimation transfer sheet having a dye-free area or In a sublimation-type thermosensitive recording method in which heat treatment is performed by an n-fold mode method via another heat treatment sheet, the length of the heat-sensitive sublimation transfer sheet or the heat treatment area of another heat treatment sheet having a region containing no dye is provided. A sublimation type thermal transfer recording method, wherein b is smaller than or equal to the length i of the dye layer region of the thermosensitive sublimation transfer sheet. 5. An image receiving sheet for sublimation transfer wherein a dye receiving layer is provided on a substrate and an over layer is further provided on the dye receiving layer, wherein ASTM D189 on the surface of the over layer is provided.
4. A sublimation transfer image-receiving sheet, characterized in that the coefficient of dynamic friction at 100 ° C. according to No. 4 is less than 0.45 and the overlayer comprises a silicone resin and a lubricating substance. 6. The image receiving sheet for sublimation transfer according to claim 5, wherein the lubricating substance is a silicone graft copolymer. 7. The image receiving sheet for sublimation transfer according to claim 5, wherein the content of the silicone resin in the overlayer is less than 85%. 8. The sublimation transfer image receiving sheet according to claim 5, wherein the thickness of the over layer is 2 μm or less. 9. The image receiving sheet for sublimation transfer according to claim 6, wherein the binder resin of the silicone graft copolymer is a dyeable resin. 10. The image receiving sheet for sublimation transfer according to claim 5, wherein a silicone oil is contained in the over layer. 11. The image receiving sheet for sublimation transfer according to claim 10, wherein the silicone oil is at least an epoxy-modified or non-modified silicone oil. 12. The image receiving sheet for sublimation transfer according to claim 10, wherein the amount of the silicone oil added is 3 to 50% by weight based on the resin of the over layer. 13. The image-receiving sheet for sublimation transfer according to claim 10, wherein the addition amount of the silicone oil is 5 to 15% by weight based on the resin of the over layer. 14. The method according to claim 10, wherein a solvent compatible with the silicone oil is contained in the overlayer forming liquid in an amount of 25% by weight or more of the total solvent of the overlayer forming liquid.
The image receiving sheet for sublimation transfer according to the above. 15. An image receiving sheet for sublimation transfer which is provided with a dye receiving layer on a substrate and further provided with an over layer on the dye receiving layer and which is applied to an n-fold mode method.
The image receiving sheet for sublimation transfer, wherein the over layer comprises a silicone resin, a lubricating substance, and an ultraviolet absorber as main components. 16. The image receiving sheet for sublimation transfer according to claim 15, wherein the content of the ultraviolet absorber is 1 to 50% by weight based on the resin of the over layer. 17. The image receiving sheet for sublimation transfer according to claim 5, wherein the substrate is a laminate in which a cushion layer is provided on paper. 18. The cushion layer is a bubble-containing plastic film, and the density D of the bubble-containing plastic film is D / Do ≦ 0.7 (Do indicates the density of a plastic film of the same material containing no bubbles). The image receiving sheet for sublimation transfer according to claim 17, wherein: 19. The image receiving sheet for sublimation transfer according to claim 5, wherein a polyethylene layer is provided on the back side of the base. 20. The card according to claim 5, wherein the substrate is a card substrate.
20. The image-receiving sheet for sublimation transfer according to any one of claims 1 to 19. 21. A heat-sensitive sublimation transfer sheet wherein the uppermost layer of the heat transfer sheet having the dye-free region according to claim 1 or another heat treatment sheet is a low dyeing resin layer. Or a sheet for heat treatment.